The present invention relates to an improved method for making 5,10,15,20-tetraphenyl-21H,23H-porphine-p-p1,p11,p111-tetrasulfonic acid, tetrasodium salt (designated p-TPPS4). The present invention is also directed to a method of making Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated p-CuTPPS4) from p-TPPS4. The improved process allows the production of p-CuTPPS4 at lower cost and higher yields compared to conventional methods of making p-CuTPPS4. The present invention further relates to a method of making 5,10,15,20-tetraphenyl-21H,23H-porphine-o,o1,o11,o111-tetrasulfonic acid, tetrasodium salt (designated p-TPPS4). The present invention is further directed to a method of making Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4) from o-TPPS4 and the use of o-CuTPPS4 as a colorant stabilizer for a variety of colorants, especially magenta colorants. The o-CuTPPS4, according to the present invention, provides a more stable and more xe2x80x9cbluexe2x80x9d colorant stabilizer compared to known colorant stabilizers, such as Cu-meso-tetra-(p-phenylcarboxylic acid)-porphine.
U.S. patent applications Ser. No. 08/757,222 filed Nov. 27, 1996; Ser. No. 08/788,863 filed Jan. 23, 1997; Ser. No. 08/843,410 filed Apr. 15, 1997; Ser. No. 08/903,911 filed Jul. 31, 1997; Ser. No. 60/055,785 filed Aug. 15, 1997; and Ser. No. 60/062,643 filed Oct. 22, 1997, all of which are assigned to Kimberly Clark Worldwide, Inc., disclose the use of a variety of porphines as colorant stabilizers. Porphines disclosed in the above-referenced applications include, but are not limited to, porphines having the following general structure: 
wherein R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO3H, 
COOH, or R1COOH wherein R1 is an alkyl group of from 1 to 6 carbons. R may also be in its corresponding 
One such porphine is Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated p-CuTPPS4) having the following structure: 
Conventional methods of making p-CuTPPS4 involve the following three-step process: 
The yield of p-CuTPPS4 in the above process is only about 10%. In addition, the resulting product comprises a mixture of porphine molecules containing from one to four sulfonic acid groups per molecule.
An attempt to make o-CuTPPS4 is disclosed in Treibs et al., Leibigs Ann. Chem., 718, 183, 1998 (hereafter, xe2x80x9cTreibsxe2x80x9d). Treibs tried to prepare o-TPPS4 from 2-formylbenzenesulfonic acid, pyrrole, and propionoic acid. However, Treibs could not isolate the resulting product. Treibs reported a yield by GLC analysis of less than about 10%.
Although porphines provide excellent light stability to all colorants, some porphines are relatively unstable and/or tend to xe2x80x9cyellowxe2x80x9d colorant compositions containing magenta dyes. A more desirable porphine molecule would be one that has less tendency to xe2x80x9cyellowxe2x80x9d a colorant composition, and moreover, to make the colorant composition more xe2x80x9cblue.xe2x80x9d
Therefore, there exists a need in the art for a convenient, low cost, high yield method of making p-TPPS4, p-CuTPPS4, and compositions containing p-CuTPPS4. There also exists a need in the art for a convenient, low cost, high yield method of making o-TPPS4, o-CuTPPS4, and compositions containing o-CuTPPS4. Further, there exists a need for improved porphines which are capable of providing superior colorant stability while being more stable and without the tendency to xe2x80x9cyellowxe2x80x9d colorant compositions containing magenta dyes.
The present invention addresses the needs described above by providing processes of making p-TPPS4 and o-TPPS4 at a lower cost and higher yields. The present invention also relates to processes of making Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated p-CuTPPS4) and Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4), and the use of p-CuTPPS4 and o-CuTPPS4 as colorant stabilizers for a variety of colorants, especially magenta colorants. o-CuTPPS4 has excellent stability and provides superior stability to a variety of colorants. Moreover, o-CuTPPS4 does not xe2x80x9cyellowxe2x80x9d magenta dyes. Consequently, less unstable dye, such as Acid Red 52, needs to be used to make a magenta composition more xe2x80x9cblue.xe2x80x9d The result is a more xe2x80x9cbluexe2x80x9d magenta color and a higher porphine to dye ratio, which creates superior light stability.
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with p-CuTPPS4 and/or o-CuTPPS4. These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.
The present invention is directed to a convenient, fast, low cost, environmental-friendly process of making p-CuTPPS4 and o-CuTPPS4. One. process of making p-CuTPPS4 proceeds by the following reaction: 
The above process produces p-CuTPPS4 at yields of about 45% compared to conventional methods of producing p-CuTPPS4, which have yields of about 20%. The result is a p-CuTPPS4 having a reduction in the cost of manufacture of approximately 50%.
The reaction conditions for the above process may vary. Typically, the reaction is carried out as follows. The reactants are mixed at room temperature. The mixture is then heated, while stirring, under reflux for about one hour. A precipitate forms during the reaction. The reaction mixture is then filtered while hot to obtain the desired p-CuTPPS4. The solid is washed with hot solvent to yield a pure product.
The choice of solvent in the above process may be any aliphatic acid having from one to six carbon atoms in the carbon chain. Suitable acids include, but are not limited to, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, formic acid, and mixtures thereof.
The present invention is also directed to a process of making Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4). The process of making o-CuTPPS4 proceeds by the following reaction: 
The above process produces o-CuTPPS4 at yields of about 55%. The resulting o-CuTPPS4 ha s excellent stability and provides superior stability to a variety of colorants. Moreover, the o-CuTPPS4 does not xe2x80x9cyellowxe2x80x9d magenta dyes. Magenta compositions containing the o-CuTPPS4 result in a more xe2x80x9cbluexe2x80x9d magenta color.
The present invention is further directed to a process of making o-TPPS4 and o-CuTPPS4 by the following reaction: 
The above process produces o-TPPS4 at yields of about 82%.
The reaction conditions for the above process may vary. Typically, the reaction may be carried out as follows. The reactants are purified by the following process or a similar purification process. The pyrrole is distilled under argon and a fraction is collected at 140xc2x0 C. The 2-formylbenzenesulfonic acid, sodium salt is purified by a Dean and Stark method using benzene as the solvent. The solution is filtered at 60xc2x0 C. and the solid pumped in a vacuum oven overnight at room-temperature. The p-toluene sulfonic acid may also be purified by a Dean and Stark method using benzene as the solvent.
The 2-formylbenzenesulfonic acid, sodium salt, N,N-dimethylformamide (DMF) and pyrrole are placed in a reaction vessel and stirred at room-temperature. The mixture is flushed with argon for about five minutes while stirring prior to heating. The mixture is then heated to 100xc2x0 C. for about ten to twelve minutes. The toluene sulfonic acid dissolved in 15 ml of DMF is injected into the reaction mixture. The reaction mixture is heated to 150xc2x0 C. and held at this temperature for about 50 minutes. The reaction mixture is then cooled in an ice bath for about 20 minutes and then poured into 1000 ml of benzene and stirred at room-temperature for about 10 minutes. The precipitate is filtered using a Buchner funnel and dried to produce a solid. The solid is then stirred in 500 ml of ethanol for about 30 minutes and filtered. The wet solid is pumped in a vacuum oven for about three hours to yield a finished product.
The choice of solvent in the above process may be any solvent, which enables the efficient production of o-TPPS4 and o-CuTPPS4. Suitable solvents include, but are not limited to, DMF and dimethyl sulfoxide (DMSO).
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with p-CuTPPS4 and/or o-CuTPPS4. Desirably, one or more of the above-mentioned colorant stabilizers are admixed with a colorant solution. The colorant stabilizer may be one or more porphines alone or in combination with at least one metal or metal salt. Optionally, the colorant stabilizer may be associated with a molecular includant, chelating agent, or other material to improve solubility and/or interaction of the colorant stabilizer and the colorant.
The p-CuTPPS4 and/or o-CuTPPS4 colorant stabilizers may be associated with a variety of dyes or colorants. A suitable dye or colorant, for example, may be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-(dimethylamino)-_-[4-(dimethylamino)phenyl]-_-phenyl-benzene-methanol}, Malachite Green Carbinol hydrochloride {N-4-[[4-(dimethylamino)phenyl]phenyl-methylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)phenyl]phenylmethylium chloride}, and Malachite Green oxalate {N-4-[[4-(dimethylamino)-phenyl]-phenylmethylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethyl-amino)-phenyl]phenylmethylium oxalate}; monoazo dyes, such as Cyanine Black, Chrysoidine [Basic Orange 2; 4-(phenylazo)-1,3-benzenediamine monohydrochloride], Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and xcex2-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloride double salt]; oxazine dyes, such as Lumichrome (7,8-dimethylalloxazine); naphthalimide dyes, such as Lucifer Yellow CH {6-amino-2-[(hydrazino-carbonyl)amino]-2,3-dihydro-1,3-dioxo-1H-benz[de]iso-quinoline-5,8-disulfonic acid dilithium salt}; azine dyes, such as Janus Green B {3-(diethylamino)-7-[[4-(dimethyl-amino)phenyl]azo]-5-phenylphenazinium chloride}; cyanine dyes, such as Indocyanine Green (Cardio-Green or Fox Green; 2-[7-[1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benz[e]indol-2-ylidene]-1,3,5-heptatrienyl]-1,1-dimethyl-3-(4-sulfobutyl)-1H-benz[e]indolium hydroxide inner salt sodium salt}; indigo dyes, such as Indigo {Indigo Blue or Vat Blue 1; 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H-indol-3-one}; coumarin dyes, such as 7-hydroxy-4-methyl-coumarin (4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258 [bisbenzimide or 2-(4-hydroxyphenyl)-5-(4-methyl-1-piperazinyl)-2,5-bi-1H-benzimidazole trihydro-chloride pentahydrate]; paraquinoidal dyes, such as Hematoxylin {Natural Black 1; 7,11b-dihydrobenz[b]-indeno[1,2-d]pyran-3,4,6a,9,10(6H)-pentol}; fluorescein dyes, such as Fluoresceinamine (5-aminofluorescein); diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxy-benzene diazonium chloride, zinc chloride double salt); phenylenediamine dyes, such as Disperse Yellow 9 [N-(2,4-dinitrophenyl)-1,4-phenylenediamine or Solvent Orange 53]; diazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)naphthalene]; anthra-quinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse Blue 14 [Celliton Fast Blue B; 1,4-bis(methylamino)-9,10-anthraquinone], and Alizarin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo Light Blue FFL or Sirius Light Blue BRR; 3-[(4-[(4-[(6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo-1-naphthalenyl)-azo]-1-naphthalenyl)azo]-1,5-naphthalenedisulfonic acid tetrasodium salt}; xanthene dyes, such as 2,7-dichloro-fluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonaphthalein dyes, such as Cresol Red (o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4-1)-[29H,31H-phthalocyanato(2-)-N29,N30,N31,N32]-copper}; carotenoid dyes, such as trans-xcex2-carotene (Food Orange 5); carminic acid dyes, such as Carmine, the aluminum or calcium-aluminum lake of carminic acid (7-a-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl-9,10-dioxo-2-anthracene-carbonylic acid); azure dyes, such as Azure A [3-amino-7-(dimethylamino)phenothiazin-5-ium chloride or 7-(dimethyl-amino)-3-imino-3H-phenothiazine hydrochloride]; and acridine dyes, such as Acridine Orange [Basic Orange 14; 3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt] and Acriflavine (Acriflavine neutral; 3,6-diamino-10-methylacridinium chloride mixture with 3,6-acridine-diamine).